Direct electrochemical defluorinative carboxylation of α-CF alkenes with carbon dioxide

• Published in: Chemical science (Cambridge) Vol. 11; no. 38; pp. 1414 - 142
• Main Authors: Gao, Xiao-Tong, Zhang, Zheng, Wang, Xin, Tian, Jun-Song, Xie, Shi-Liang, Zhou, Feng, Zhou, Jian
• Format: Journal Article
• Language: English
• Published: 07.10.2020
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/d0sc04091f

An unprecedented γ-carboxylation of α-CF 3 alkenes with CO 2 is reported. This approach constitutes a rare example of using electrochemical methods to achieve regioselectivity complementary to conventional metal catalysis. Accordingly, using platinum plate as both a working cathode and a nonsacrificial anode in a user-friendly undivided cell under constant current conditions, the γ-carboxylation provides efficient access to vinylacetic acids bearing a gem -difluoroalkene moiety from a broad range of substrates. The synthetic utility is further demonstrated by gram-scale synthesis and elaboration to several value-added products. Cyclic voltammetry and density functional theory calculations were performed to provide mechanistic insights into the reaction. A γ-carboxylation of α-CF 3 alkenes with CO 2 using platinum plate as both working cathode and nonsacrificial anode has been developed.